Method for controlling pests and agents therefor



United States Patent 3,197,363 METHOD FOR ZUNTRGLLEQG PEd'iS AND AGENTS THEREFGR Kurt Gubler and Enrico Knusli, Riehen, near Basel, Switzeriand, assignors to 3. R. Geigy A.-G., Basel, Switzeriand No Drawing. Original application May 9, 1962, Ser. No. 193,598. Divided and this application Aug. 2, 1963, Ser. No. 31%,514 Claims priority, application Switzerland, May It 1961, 5,503/61 7 Claims. (Cl. 167-39) The present invention is concerned with new pest control agents which are excellent active ingredients for the combatting of fungi, especially phytopathogenic fungi and in addition, can also have insecticidal, nematocidal, acaricidal and bastericidal activity, i.e. compositions containing same as well as methods for using the active ingredients.

Examples of plant diseases which can be eifectively controlled or combatted with the new active substances are: downy mildew (Plasmospora viticola) for example on grapes, powdery mildew (Erysiphe) for example on wheat and cucumbers, grey mould (Botrytis cinerea) for example on Vicia faba plants etc.

It has surprisingly been found that new thiocyanophenyl derivatives of the formula wherein each of R and R independently is hydrogen or halogen e.g. chlorine, bromine, especially chlorine, lower alkyl (1 to 4 carbons) e.g. methyl, isopropyl etc. alkyenyl containing 2 to 3 carbons, e.g. allyl, alkoxy containing 1 to 4 carbons e.g. methoxy etc. or nitro,

R is alkyl containing 1 to 8 carbons e.g. methyl, ethyl, isopropyl, butyl, amyl, octyl etc., alkenyl containing 2 to 4 carbons e.g. allyl, crotyl, butenyl, halogenated alkyl containing 1 to 4 carbons e.g. chloroethyl etc., halogenated alkenyl containing 2 to 3 carbons e.g. dichloroallyl etc. and alkinyl containing 3 carbons e.g. propargyl,

R is hydrogen, or methyl, preferably hydrogen,

n and m independently are zero or one (if n is one In should preferably also be one), are excellently active ingredients for the combatting of fungi, in particular phytopathcgenic fungi and, in additon, can also have insecticidal, nematocidal, acaricidal and bactericidal activity.

The new compounds per se are disclosed and claimed in parent application Serial No. 193,598, filed May 9, 1962, of which the present application is a division.

The new active ingredient sot Formula I can be' appropriately divided into four subgeneric formulae:

(a) Aromatic-aliphatic diesters of carbonic acid having the formula Noso-oooss B2 II wherein R R and R have the meanings given above (n is zero and m is one, in relation to Formula I).

3191 Patented July 27, 1965 ice These compounds of Formula II are good fungicides and are also especially valuable for their insecticidal activity, e.g. against mosquitos, gnats of the genus Aedes,

(b) Thiocyanophenol esters of aliphatic, saturated or unsaturated monocarboxylic acids having the formula NCS OCOR3 R2 111 wherein R R and R have the meanings given above (and n and m are both zero, in relation to Formula I).

These compounds of Formula III are good fungicides. (c) Esters of aliphatic thiocyanophenoxy monocarboxylic acids having the formula NCS- O(i3H-COORs R4 R: IV

wherein n and m are each one (in relation to Formula I), and

R R R and R have the meanings given above.

These compounds of Formula IV besides having a fungicidal activity have a very pronounced acaricidal activity, e.g. against the common red spider (Tetranyclzus urticae); and

(d) Aliphatic thiocyanophenoxy ketones having the formula wherein R R and R have the meanings given above, R is alkyl having 1 to 4 carbons (n is one and m is zero, in relation to Formula I).

Compounds of Formula V are good fungicides.

The new active ingredients of Formula I and the more specific Formulae H to V can be produced by the methods known from the literature. If desired substituted 4-thiocyanophenols produced by known methods, are used as starting materials. These can be converted with phosgene, for example in solution in the presence of an inorganic or organic base, into the corresponding chloroformic acid esters and then reacted with, if desired, chlorinated lower alkanols, alkenols or alkinols to form diesters of Formula II. Benzene, ethyl acetate or ether etc. can serve as solvents for this reaction.

Active ingredients of Formula III are obtained, for example, if the starting phenols are heated with lower molecular aliphatic monocarboxylic acid chlorides or bromides in the presence of basic substances, either direct or in organic solvents. Active susbtances of the Formula IV are obtained, for example, by reacting the starting phenols with halogen acetic acidor a-halogen-propionic acidalkyl alkenyl or alkinyl esters. This reaction can be performed in organic solvents such as benzene or acetone, in the presence of potash or of tertiary amines. Finally, active ingredients of Formula V are obtained if, in the reaction described immediately above, the corresponding halogen ketones are employed instead of the halogen acetic or a-halogen propionic acid esters. If a chlorocar- A mixture of 13 parts of 3-methyl-4-thiocyanophenol, 12.6 parts of calcined potassium carbonate, 1.9 parts of potassium iodide, 9.5 parts of crotonic acid chloride and 200 parts by volume of acetone are refluxed for 12 hours. The product is worked up by filtering off the precipitate, evaporating off the acetone and dissolving the residue in ether. The ethereal solution is treated three times with 50 parts by volume or" ice. cold 2 N sodium hydroxide solution and then washed neutral with water. The solution, dried with sodium sulphate, is concentrated and the residue is purified by distillation. The pure product, crot-onic acid-(3-methyl-4-tl1iocyano)-phenyl ester, clistills under high vacuum at 116.7-120 C. under a pressure of 0.0001 mm. Hg.

Example 2 16.5 parts of 2-methyl-4-thiocyanophenol, 16 parts of calcined potassium carbonate, 13 parts of chlorocarbonic acid ethyl ester and 200 parts by volume of benzene are refluxed together for 12 hours. The product is Worked up by diluting with benzene, shaking three times with 50 parts by volume of ice cold 2 N sodium hydroxide solution each time, washing three times with 100 parts by volume of water each time and evaporating oit the henzene. After recrystallising twice, the O-(2-methyl-4- thiocyanophenyl)-O-ethyl carbonate melts at 445-47.

Other active ingredients of the general Formula I are given below which can be produced by one of the methods described above.

-( 3-rnethyl-4-thiocyanophenyl) -O'-ethy1 carbonate,

311, 123-125 0- (4-thiocyanophenyl) -O-ethyl carbonate,

B.P., 136-13 3 0- 3 -methyl-4-thiocyanophenyl) -O-methyl carbonate,

B.P. ,=122-124, O- 3-methyl-4-thio cyanophenyl) -O'-isopropyl carbonate,

M.P., 53-56 O-( 3-methyl-6-isopropyl-4-thiocyanophenyl) -O-ethyl carbonate,

B.P.0'001: o O-( 3 -methyl-4-thiocyanophenyl -O-n-butyl carbonate,

B.P.0 0g9= o 0- 3-methyl-6-isopropy1-4-thiocyanophenyl) -O-allyl carbonate, O-( 3-methyl-6-isopropyl-4thiocyanophenyl -O-methyl carbonate,

Es -0 034 1 O-( 3 -methyl-6-isopropyl-4-thiocyanophenyl) -O-n-butyl carbonate,

B.P.0 o 9=155156, O- 3 methyl-4-thiocyanophenyl) -O-n-amyl carbonate,

B.P. 156-158 0- 2-methyl-4-thiocyanophenyl -O'-isopropy1 carbonate,

B.P. m9= 3 o O-( 2-methyl-4-thio cyanophenyl -O-n-butyl carbonate,

-0.00a= 156 O-'( 2,6-dichloro-4-thiocyanophenyl -O'-ethyl carbonate,

M.P., 69-71 0- 2-nitro-4-thio cyanophenyl -O'-ethyl carbonate,

M.P., 53-565 Croto nic acid- 2-methyl-4-thiocyano) -phenyl ester,

B.P.b =122.5-125.5

Crotonic acid-(4-thiocyano -phenyl ester,

M.P., 46.5-50 Acetic acid- 3 -methyl-4-thiocyano -pl1enyl ester,

M.P., 48-50 (3 -methyl-4-thiocyanophenoxy -acet-ic acid ethyl ester,

M.P., 52-53 (3 -methy1-6-isopropyl-4-thiocyanophenoxy) -acetic acid ethyl ester,

M.P., 61-645 (3 -methyl-6-isopropyl-4-thiocyanophenoxy) -acetic acid methyl ester,

M.P., 57.5-59 (3-methyl-6-is opropyll-thiocyan ophenoxy) -acetic acid p-chloroethyl ester,

3.1 186-189 (3 -methyl-6-isopropyl-4-thiocyanophenoxy -acetic acid-is opropylester,

B.P.0 O2:165170, (3 -methyl-6-isopropyl-4-thiocyanophcnoxy) -acetic acid-w propylester,

B.P. =144.5-148 (3-methyl-6-is opropyl-4-thiocyanophcnoxy) -acetic acid- 2,3-dichloro) -.allyl ester,

B.P.Q01:203 (3 -methyl-6-isopropyl-4-thio cyanophenoxy) -acetic acid-buten-( 2 ylester, (3 -methyl-6-isopropyl-4-thiocyanophenoxy -acetic acid-propargyl ester,

B.P.U G2= a (3 -rnethyl-6-isopropyl-4-thiocyanophenoxy) -a cetic acid-n-octyl ester,

B.P. =212-217 (3-rnethyl-6-isopropyl-4-thiocyanophenoxy) -acetic acidn-butyl ester,

B-P- (L03: a- 3-methyl-6-isopropyl-4-thiocyanophenoxy -propionic acid ethyl ester, (3-methyl-6-isopropyl-4-thiocyanophenoxy) -acetic acidallyl ester,

B-P. 0 01: o (Z-methyl-4-thiocyanophenoxy) -acetic acid-isopropyl ester,

B-P. 0 00 138-140 2-methyl-4 thiocyanophenoxy -a cetic acid-allyl ester,

B.P. (L006: O 2-metl1yl-4-thiocyanophenoxy acetic acid-B-chloroethyl ester,

B-P. 0 2: (3-methyl-4-thiocyanophenoxy) -a-cetic acid-methyl ester,

MP. :68 4-thiocyanophenoxy-acetic acid-ethyl ester,

B.P. :l64-165.5 2-nitro-4-thiocyanophenoxy -acetic acid-ethyl ester,

M.P., 65.5 (2-methyl-4-thiocyanophenoxy)-acetic acid-n-octyl ester,

B-P. (L003: 183-1S4 (2-isopropyl-4-thiocyanophenoxy) -acetic acid-ethyl ester,

B.P. 168-170 (2-allyl-6-methyl-4-thiocyanophenoxy -acetic acid-ethyl ester, (3-methoxy-4-thiocyanophenoxy -acetic acid-ethyl ester, 1- (2-methyl-4-thiocyanophenoxy) -acetone,

The phytoxicity of the new active ingredients is slight.

The new active substances can be used as such or in combination with suitable carriers, or adjuvants i.e. usual pulverulent, semi-solid (salve-like), liquid, gaseous carriers, diluents and/or distributing agents. The adjuvants should be non-basic i.e. neutral or acidic. They are suitable in the first place for the protection of plants and parts thereof from attack by injurious fungi, but they can also be used for the treatment of organic materials such as, eg Wood, furs and leather. Some of the new active in gredients can also be used as insecticides (Formula II) or as acaricides (Formula IV).

The new active ingredients can be applied in solid form, for example, as finely pulverised dusts or sprinkling agents, sometimes also as granulates, and also in liquid form as emulsion, suspension, spray suspension or solution.

For example the new active substances can be combined with solid pulverulent, preferably non-basic carriers such as, for example, talcum, kaolin, bole, bentonite, chalk, ground limestone, and if desired, the pulverulent fungicides obtained can be made suspendable in water by the addition of wetting and dispersing agents. The active substances can also be dispersed in water with the aid of suitable emulsifying agents or they can be dissolved in organic solvents, for example, in chlorinated hydrocarbons such as trichloroethyelne or in medium petroleum frac' tions, this possibly with the addition of auxiliary solvents such as acetone, higher ketones or dimethyl formamide. After the addition of suitable emulsifying agents, e.g. of aromatic polyglycol ethe s, mixtures with auxiliary solvents can be worked up with water into emulsions. The active substances, however, can also be distributed in the air in the form of aerosols, smoke or steam, particularly for example, in storerooms and greenhouses.

Dusts suitable for application of the active substances according to the invention can be produced, for example, by mixing or milling together the active substances with a solid carrier. As such can be used: talcum, diatomaceous earth, kaolin, bentonite, calcium carbonate, hon'c acid or tricalcium phosphate. On the other hand, the substances can also be brought onto the carriers by means of a volatile solvent.

To produce emulsions, the active substances as such or after dissolving them in organic solvents such as, e.g. xylene, can be emulsified in water which contains a capillary active substance. For practical application however, it is generally more advantageous first to combine liquid active substances with capillary active substances or to combine solid or liquid active substances with inert organic solvents and capillary active substances to produce concentrates which, in their turn, are single phase systems, i.e. solutions or multi-phase systems; these can then be worked up with water into ready-for-use emulsions. As capillary active substances, non-ionogenic substances such as, e.g. polyethylene glycol ethers of fatty alcohols or of dialkyl phenols and polycondensation products of ethylene oxide can be used. Cyclic hydrocarbons such as benzene, toluene or, particularly, xylene, and also ketones such as acetone, butanone, cyclohexanone or methylcyclohexanones are suitable, for example, as solvents for the production of emulsion concentrates.

Suspensions can be obtained by suspending Wettable powders in water, which powders are produced in their turn by combining solid active substances with capillary active substances or combining solid or liquid active substances with solid pulverulent carriers and capillary active substances.

In addition, the active substances produced according to the invention can also be dissolved in organic solvents, for example in chlorinated hydrocarbons such as trichloroethylene or in medium petroleum fractions, possibly with the addition of auxiliary solvents such as acetone or higher ketones. Finally, the active substances can be dispersed in the air also, in the form of aerosol, smoke or mist, this particularly in storerooms or greenhouses.

To increase the duration of action, it is sometimes advantageous to add suitable stabilizers either before or after the active substances are combined with the carriers. Epoxides may be employed as, e.g. epichlorohydrin, cyclohexenoxide, styrene oxide, glycide ethers such as 1- phenoxy-2,3-epoxypropane, or 1,[3-naphthoxy-2,3-epoxypropane. Other stabilizers, however, may be employed to increase the stability of the active substances according to the invention.

If desired, the biological activity of the agents according to the invention can be supplemented by the addition of insecticidally, nematocidally or other fungicidally active substances. A combination with other plant protection agents or with any additives desired which influence the fungicidal action in any particular direction is also possible.

Some typical forms of application are given in the following examples. Parts are given therein as parts by weight:

Example 3 2-5 parts of active substance, e.g. O-(2-methyl4-thiocyanophenyl)-O-ethyl carbonate are ground with 98-95 parts of talcum. The dust so obtained is an active disinfectant, for example, for seed bed earth and also for plants or parts thereof such as bulbs and tumours.

Example 4 On milling together 10 parts of active substance, e.g. acetic acid-(3-mcthyl-4-thiocyano)-phenyl ester, 82 parts of kaolin or chalk and mixing with 8 parts of wetting and dispersing agents, e.g. 8 parts of sulphite waste liquor, a concentrate is obtained which, on mixing with water, produces a fungicidal and acaricidal spray which is excellently suitable for the treatment of the parts of plants above the ground.

Example 5 20 parts of crotonic acid-(4-thiocyano)-pheny1 ester, 50 parts of xylene and 30 parts of ethylene oxide con densation products of alkyl phenols are mixed together to obtain a concentrate which can be used for the preparation of emulsions. The emulsions so obtained can be used for combatting fungi diseases on plants.

A concentrate for the production of less Wetting emulsions is obtained by mixing 25 parts of crotonic acid-(4- thiocyano)-phenyl ester, 67 parts of xylene and 8 parts of a polyethylene oxide esterified with ricinus oil.

Example 6 Bean leafs infested by imagines, larvae and eggs of the common red spider (T etranychus urticae) were sprayed with a 0.01% emulsion of (3-methyl-6-isopropyl-4-thio cyanophenoxy) acetic acid n-propyl ester. After 3 days all larvae and imagines were completely killed. With a 0.1% emulsion of said active compound, after 6 days there was a 100% destruction of the eggs. The same results are obtained if Phencapton resistant red spiders are used in the test.

Example 7 wherein R and R are independently selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl, alkenyl containing 23 carbon atoms, alkoxy containing 1-4 carbon atoms and nitro,

R is a member selected from the group consisting of alkyl containing 1 to 8 carbon atoms, alkenyl containing 2-4 carbon atoms, chloro alkyl containing 1 to 4 carbon atoms, chloro alkenyl containing 23 carbon atoms and propargyl,

R is a member selected from the group consisting of hydrogen and methyl, and m is independently a number from zero to one inclusive. 2. Method for controlling pests which comprises contacting the pests with a pesticidal composition comprising as an active ingredient a compound of the formula wherein R and R are independently selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl, alkenyl containing 2-3 carbon atoms, alkoxy containing 1-4 carbon atoms and nitro,

R is a member selected from the group consisting of .alkyl containing 1 to 8 carbon atoms, alkenyl containing 2 to 4 carbon atoms, chloro alkyl containing 1-4 carbon atoms, chloro alkenyl containing 2-3 carbon atoms and propargyl,

R is a member selected from the group consisting of hydrogen and methyl and m is independently a number from zero to one inclusive.

3. A pesticidal composition comprising as an active ingredient a pesticidally effect amount of a compound of the formula R4 Rx wherein R and R are independently selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl, alkenyl containing 2-3 carbon atoms, alkoxy containing 1-4 carbon atoms and nitro,

gs U

R is a member selected from the group consisting of alkyl containing 1 to 8 carbon atoms, alkenyl containing 2-4 carbon atoms, chloro alkyl containing 1 to 4 carbon atoms, chloro alkenyl containing 2 to 3 carbon atoms and propargyl,

R is a member selected from the group consisting of hydrogen and methyl and m is independently a number from zero to one inclusive, and an adjuvant as a carrier, said adjuvant being selected from the group consisting of neutral and acidic solid pulverulent, liquid and gaseous agriculturally acceptable carriers.

4. Method for controlling pests which. comprises contacting the pests with (3-methyl-6-isopropyl-4-thiocyanophenoXy)-acetic acid methyl ester.

5. Method for controlling pests which comprises contacting the pests with (3-met11yl-6-isopropyl-4-thiocyanophenoxy)acetic acid n-propyl ester.

6. A pesticidal composition comprising as an active in redient a pesticidally effect amount of (3-metl1yl-6- isopropyl-4-thiocyanophenoxy)-acetic acid methyl ester, and an adjuvant as a carrier, said adjuvant being selected from the group consisting of neutral and acidic solid pulverulent, liquid and gaseous agriculturally acceptable carriers.

7. A pesticidal composition comprising as an active ingredient a pesticidally eflect amount of (3-methyl-6- isopropylt-thiocyanophenoxy)-acetic acid n-propyl ester, and an adjuvant as a carrier, said adjuvant being selected from the group consisting of neutral and acidic solid pnlverulent, liquidand gaseous agriculturally acceptable carriers.

References Qitcfi by the Examiner UNITED STATES PATENTS 2,866,804 12/58 Nischk et al 260454 JULEAN S. LEVITT, Primary Examiner. 

1. METHOD FOR CONTROLLING PESTS WHICH COMPRISES CONTACTING THE PESTS WITH A COMPOUND OF THE FORMULA 